Boron compounds



BQRUN CGMPUNDS Donald l). Einriclr, Shaker Heights, Ghia, assignor to 'I lre Standard Gil Company, Cleveland, Ohio, a corporation of Ohio No Drawing. Filed Dec. 3l), 1960, Ser. No. 79,538 5 Claims. (Cl. 260--404) This invention relates to novel boron compounds. More particularly, this invention relates to a class of boron compounds which may find use as additive-s for motor fuel, fuel oil, and lubricating oil compositions..

The boron compounds of this invention are .prepared .by reacting boric acid or boric oxide with an N-acylated amino hydroxy compound having the Ifollowing general formula:

n l Rl-C-NH-(IJ-R:

wherein R1 represents a radical selected from a group consisting of an alkyl, alkenyl, or arylalkyl radical containing 7 to 21 carbon atoms, R2 'represents the radical -(CH3)nOH where n is a small Whole number such as l to 3, and R3 represents a radical selected from the group consisting of R2l or anI alkyl radical containing l to 8 carbon atoms where R3 may be same or different for the two positions of R3 on the molecule.

When both positions of R3 are the same Ias R2, the boron compounds wil-l have the general structure:

u (CHnO Rl-o-NH-o-(cnnnoqa (CHzlnO When one position for R3 is the same as R2 and the other position for R3 is an alkyl radical, the boron'cornpounds will have the general structure:

R3 (CH2)n-O (CH2) n-O B--OX where X is hydrogen or When both positions for R3 are alkyl radicals, the boron The above-mentioned class of boron compounds have been found to be excellent multi-functional additives for motor fuel when one or more of the same are incorporated therein in only small amounts.l In common with other boron-containing compounds, these materials are highly effective in controlling troublesome conditions caused by deposit buildup in the combustion cham-ber of yan internal combustion engine.

I The amount of boron compound or compounds to be used in motor fuel may vary. Genenally the smallest amount that will give significant results will be in the lorder of 0.001% by weight. Amounts greater than ap- 3,080,403 Patented Mar. 5, 1953 proximately 1% by weight usually cannot be justified economically. y

The amount of boron compound to be added to the lubricating composition may vary. Best results are obtained when Iamounts of at least 1% by weight are used. Amounts greater than 10% will usually not be justified economically.

The N-acylalted amino hydroxy compounds used in preparing the boron compounds of this invention may be prepared fromv amino hydroxy compounds containing a primary or secondary amine functional group by the N-acyliation of the amine group of the compound with a long-'chain acid or acid-chloride containing from 8 to 22 carbon atoms, and such materials are well known in the trade and are commercially available.

Any of the compounds having the general formula offered hereinbefore lare suitable for the invention. The preferred compounds, however, are the N-acylation products of amino dihydroxy compounds so that one position fior R3 is the same as R3 and the `other position for R3 is an alkyl radical, :and where R1 as defined heretofore contains from 11 to 17 carbon atoms for maximum solu-bility in the liquid hydrocarbon. The amino dihydroxy compounds are preferred since they are more readily soluble in hydrocarbons than are 'the amino trihydroxy compounds where R3 for both positions on the molecule are the same as R3 and because thelarnino dihydroxy compounds such as of the type derived from 2-amino-2` alky1propanediol1,3 form a six-membered ring upon boration with boric acid or boric oxide which is believed to offer optimum stability toward hydrolysis. Mixtures of the amino hydroxy compounds may be used. Mixtures of radical-s may also be used for R1, and this frequently will be the case since the R1 radicals are pre-ferably derived from fatty Iacids found in naturally occurring `fats and oils, and hence, R1 will correspond to the fatty `acid radicals derived from fats and oils such as tallow, cottonseed oil, soybean oil, tall oil, etc. The nature of R1 does not affect the results appreciably, it has been found, and therefore its selection will be dictated largely by economics. The commercial grade of the compounds, including small amounts of impurities or by-products, are suitable. A'particularly desirable starting compound for purposes of the invention is the N-oleoylamide of 2-amino-Z-methylpropanediol-1,3

These N-acylated amino hydroxy compounds readily undergo reaction with boric acid un-der conditions in which the water of reaction may be removed from the reaction mixture as it is formed. This removal of water ym-ay be accomplished by simple boiling, but it is preferable -to remove the water by means of azeotnopic fractional distillation using, preferably, benzene or toluene as Example 1 74.4 grams of N-oleoylamide of Z-amino-Z-methyl propanediol-l,3 was placed in a flask with 12.4 grams boric acid (a 1:1 molar ratio) and 120 milliliters (ml.) of benzene. The mixture was stirred and refluxed together until 7.3 ml. of water was azeotropically distilled olf overhead. The reaction mixture was then ltered and the filtrate evaporated down to produce a transparent plastic material which was readily soluble in gasoline. The reaction proceeds in accordance with the following equation:

ratio). The mixture was refluxed together for several hours until 8.0 ml. of water was azeotropically distilled oif overhead. The remainder of the benzene was then distilled 01T, leaving a plastic solid which was readily soluble in gasoline. The reaction may be represented by the following equation:

gasoline. The reaction that took place may be represented by the following equation:

0 H CH:

CHnOH Hr-O As stated heretofore, the boron compounds of this invention are stable toward hydrolysis and particularly so when dissolved in gasoline.

This application is a continuation-impart of my application Serial No. 836,948, led August 31, 1959, now U.S. Patent 3,009,791, issued November 21, 1961, in which there was a requirement for restriction and in which the following claims were not elected.

(1? CH3 CHOH H Cga /CHz-O\ O-CH; CH: (l) 2CH35-CNHC 2H=BO3 CnHa-d-NH-C B-oB C-NH-o-CnHas-rsmo CBzOH CH3-O O-CHa Example 3 30 I claim: 1059 grams of the N oleoylamide of 2 amin0 2,2 di -1. A boron compound selected from the group consistmethyl propanol was placed in a ask with 6.2 grams of mg of' boric acid (3:1 molar ratio) and 300 m1. of benzene. The (n) Rs (CH2M-0 mixture was stirredV and reuxed together until 5.4 ml. of R, C NH B OX water was azeotropically distilled olf overhead. The re- (OH) o maining benzene was then distilled oil, leaving a plastic product readily soluble in gasoline. The reaction proceeds where X is selected from the group consisting of hydrogen as follows: and

te t CH2-(|7-NH-C-CWH33 l) CH3 /B\ o CH3 CH3 u CH, /0 0\ CH3 tl? 3C17Hs3-C--NH-C -l- HSBC; HsaCu-C-NH-(lJ-CH: CHr-C-NH-C-CHHM 3H2O CHzoH CH; H

Example 4 50 (l) 38.5 grams of the N-oleoylamide of tris(hydroxy /0-(OH2L. R methyl) aminomethane was dissolved in 300 ml. of ben- B C NH C R, zene. 6.2 grams of boric acid was then added (a 1:1 \O(CH) 2 n molar ratio) and the mixture was reuxed at the azeo- (2) tropic distillation temperature for the removal of the theo- (CH) O retical amount of water with benzene overhead. The n y n remainder of the benzene was distilled oft'. The reaction RfC-NH-C-(CHlnO-B proceeds according to the following equation: (03,)0

n onion and clyHaa-o-NH-c4CHiOH-rntoa (3) R o 3 CHzOH ll H /CHz-0\ (CH2)n-l *NH-C-Rx Ci'IHsa-C-NH-C-CHg-O-B-i-BHZO 65 (l) R3 CH o B 0 R3 0 0 R3 Emmp'e 5 R .l N.. t or s.. e. N.. t R 20.7 grams of the n-phenylacetylamide of 2-amino-2- 1*( 2) D"- l methylpropanedioll,3 was placed in a ask with 12.4 70 R2 3 grams of boric acid (a 1:1 molar ratio). The mixture was wherein R1 represents a radical selected from the group reuxed until 3.6 ml. of water was azeotropically distilled consisting of an alkyl, alkenyl, and arylalkyl radical conoi overhead as an azeotrope with benzene. The retaining 7 to 21 carbon atoms, n is a small whole number mainder of the benzene in the flask was then distilled ott, from 1 to 3, and R3 where present for one position on .leaving a white solid which was moderately soluble in the molecule, represents an alkyl radical containing 1 to 8 carbon atoms and when present for more than one position on the molecule the R3s represent members selected from 'the group consisting ofthe same and different alkyl radicals containing 1 to 8 carbon atoms.

2. A new compound having the formula:

O Ra/(CHa)n-O (CHM-O 0-(CHz)n wherein R1 represents a radical selected from the ygroup consisting of an alkyl, alkenyl, and arylalkyl radical containing 7 to 2l carbon atoms, n is a small whole number from 1 to 3, and R3 represents an alkyl radical containing l to 8 carbon atoms.

4. A new compound having the formula:

wherein R1 represents a radical selected from the `group consisting of an alkyl, alkenyl, and arylalkyl radical containing 7 to 21 carbon atoms `and n is a small whole number from l to 3.

5. A new compound having the formula:

wherein R1 represents a radical selected from the group consisting of an alkyl, alkenyl, and arylalkyl radical con taining 7 to 21 carbon atoms, n is a small whole number from l to 3, and the R3s represent members selected from the group consisting of the same and different alkyl radicals containing 1 to 8 carbon atoms.

References Cited in the le of this patent UNITED STATES PATENTS Pigott Aug. 25, 1936 Gillman May 4, ,1948

UNITED STATES PATENT oFEICE l CERTIFICATE 0F CORRECTION Patent No. 3,080,403 March 5, 1963 Donald D. Emrick It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letter-s Patent should read as corrected below.

Column l, lines 5l to 59, the formula should appear as shown below instead of as in the patent:

R3 B 3 O\ T Rl-C-NH- -cH2 n fcHgM----N -Rl R3 R3 columns 3 and 4, lines 22 to 28, the formula should appear as shown below instead of as in the patent:

column 5, lines l to 19, the formula should appear as shown below instead of as. in the patent:

(CH2) 'n-o o-(cH2 Signed and sealed this 24th day of December 1963.

(SEAL) Attest: A ERNEST W. SWIDER EDWIN L. REYNOLDS Attesting Officer Acting Commissioner of Patents 

1. A BORON COMPOUND SELECTED FROM THE GROUP CONSISTING OF: 